Compound of the pyrazolanthrone series and process of making same



Patented Nov. 11, 193i) STATES TET IFFECE HEINZ SCHEYER, 'RIO JANEIR-O, BRAZIL, ASSIGNOR TO GENERAL ANILI NE WORKS, INC., OF NEW YORK, N. Y., A CORPORATION OF DELAVTARE COMPOUND on THE PYRAZOLANTHRONE SERIES nivnignoonss OF MAKING SAME No Drawing. Application filed April 11, 1929, Serial No. 354,433, and in- Germany April 5, 1928.

wherein R stands for hydrogen or an alkyl radicle and R stands for a residue of anaromatic hydrocarbon which may be substituted by halogen. My new compounds are obtainable from a l-halogen-anthraquinone-Q-oarboxylic acid in the following manner:

l-halogen-anthraquinone-2-carboxylic acid is at first caused to react with hydrazine, pref- ,erably while heating and in the presence of a suitable diluent such as, pyridine. As an intermediate probably anthraquinone-l-hydrazine-Q-carboxylio acid is formed and then 'ringclosure of the hydrazine group occurs, surprisingly with the ketogroup standing in the 9-position of the anthraquinone nucleus, not with the carboxylic acid group of the 2- position. The pyrazolanthrone-2-carboxylic acid thus formed is then converted into its 5 acid chloride according to oneof the usual methods and the pyrazolanthrone-Q-carboxylic acid chloride is condensedwith an aromatic hydrocarbon or a halogenated substiw tution product thereof, which compounds in the following claims are defined as aromatic hydrocarbon compounds, in the presence of an acid condensing agent, such as aluminium or iron chloride. r 4:5 The probable course of the reactions in the combined process may be illustrated by the following equations:

HzN

0 Hal l l 4 coon -b i hydrazine l-halogenanthraquinone- 2-carb0xylic acid NNH pyrazolahthrone-Zcarboxylic acid chloride intermediate, not

isolated pyrazolanthrone- 2-carboxylic acid NNH v I I l i C 0.ary1 V 2-aroyLpyrazo1anthrone In all these formulas the anthraquinone nucleus as well as the aryl residue may contain further substituents.

The pyrazolanthrone-2-carboxylic acid may be further on alkylated 0r aralkylated at the nitrogen atoms of the pyrazol ring according to one of the usual methods. WVhen converting the thus obtained compounds into concentrated sulfuric acid'with a yellow to 'orangecolor, in an aqueous alcoholic caustic alkali solution with a violet color; they form with an alkaline hydrosulfite' solutiona reddish vat. The new compounds are important intermediates for theproduction 'of dyestuffs.

In order to further illustrate my invention the following examples are given, the parts bein b wei ht and all tem Jeratures in centigrade degrees; but I wish it toibe understood that my invention is not limited to the examples given, nor to theexact conditions st'atedtherein. r V

E mample 1 14 ,3 parts of 1-chl0roranthraquinone2: carboxylic acid are dissolved'in 60 parts of hot dehydrated pyridine and at aboutl' l above 300.

tone of the}, probable formula:

l V t The new pyrazolanthrone 2 carboxylic acid is soluble in a solution of'carbonate of soda with a yellow, in a caustic soda solution with a red color, in: concentrated sulfuric acid withan orange color; its melting point is 7 2,6 parts thereof are finely suspended in about 26 parts of ,trichlorobenzene, ,4" parts of thionylchloride are added andthemixture is heated to feebly boiling until a total solution is formed. The acid chloride thus formed is freed from the solvent and added to 30parts of toluene. To the suspensio-nthus obtained 3 :parts of finelv divided aluminium chloride are added and the mass is heated while stirring to about 80 and-kept at this temperature, until the evolution. of hydrochloric'acid has-ceased. The cooledreaction mass is poured on-ice, some hydrochloric-acid is added and theexcess-of toluene is expelled by steam... The tolyl-2-pyrazolanthronylke' V l ve 33 l is thus obtained as a yellow powder. It may befreed from some unchanged carboxylic acid ibyboiling with asolution ofcarbonate of "soda; I The new ketone compound dissolves in an aqueous alcoholic caustic soda solution with an intense violet color. scarcely soluble in an aqueous alkali solution. Thecoloration of the solution in concentrated sulfuric acid is orange. After purifying the'eompound by one recr'ystallization from monochlorobenzene it shows a melting point of about 250 C. 7

When replacing toluene by a correspond ing quantity of'para-diachlorobenzene a di-' i chlorO-benzoyl-2-pyrazolanthrone of the I probable formula V is obtained of similar properties as described above. After once recrystallizingit from monochlorobenzene' it has a .melt-ingypointi of I about 297 C; The coloration of the solu-- tion in analcoholic caustic soda solutionyis somewhat; more =bluishviolet than that of; a solution of toluyl-2-pyrazolanthrone;1;- The product derivedv from 'pyrazolanthrone-fzcarboxylic acid chloride and QA-dichlorotoluene is very similar'tothat obtained when using para-dichlorobenzene.

Example $2:

The pyrazolanthroneg2carboxylic acid obtainable as describedin Example 1 is treated with dimethylsulfate in an alkaline solution.

2,8 parts of N methylpyrazolanthroneficarboxylic acid thus obtained are boiled after addition, of 3 parts of thionyl'chloride and about 40 parts'of toluene until a complete solution is formed' WVhen cool the acidchloride separates in the form offine needles.

When treating this acidchloride with toluene and aluminium chloride in the manner dcscribed inE'xamplelanewN-1nethyl 2-toluyl pyrazolanthrone is obtained; It crystallizes from glacial acetic acid in the form ofyels low' needles of about 250 melting point.

With an alkaline hydrosulfite 'solution it formsa bluish red vatdyeing cotton .thereflOHlfGBblB yellow shades.

The production; of the ketone compound may bealso carriedIout without isola'tinggthe acid chloridel The; same productgis obtained vwhentr-eating subsequently the 2-toluylpyrazolanthrone described in Example 1 with dimethy lsulfate in. an alcoholic alkaline solution.

1. A processwhic'h comprisestreating an 1-halogen-anthraquinone 2 carboxylic acid with hydrazine, converting the pyrazolane th1'one-2-carboxylic acid thus fo'rmedinto its chloride and condensing this, chloridewith an aromatic hydrocarbon compound.

2. A process which comprises treating an wherein R means hydrogen or alkyl and R stands for a residue of an aromatic hydrocarbon which may be substituted by halogen. 5. As new products keto-compounds of the pyrazolanthrone series corresponding probably to the general formula:

CO-phenyl wherein R means hydrogen or alkyl.

6. As a new compound a Q-(dichlorobenzoyl) -pyrazolanthrone of the probable formula NN'H l soluble in an aqueous alcoholic caustic soda solution with a bluish intense violet color, in concentrated sulfuric acid with an orange color.

In testimony whereof, I aflix my signature.

HEINZ SOHEYER. 

